Diesel fuel oils



Patented Nov. 8, 1949 2,487,189 DIESEL FUEL'OILS HerschelG. Smith, Wallingford, Troy L. Cantrell,

Lansdowne, and Mark L. Hill, Yeadon, Pa., assignors to Gulf Oil Corporation, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Application May 28, 1946,

a Serial No. 672,910

2 Claims. 1 4

This invention relates to improved Diesel fuel oils and more particularly to Diesel fuel oils which contain small amounts of addition agents which improve the performance characteristics of Diesel engines that burn said improved Diesel fuel oils.

Diesel engines are generally operated with fuel oils that have a boiling range above that of gasoline and below that of a motor lubricant. They may for instance have initial boiling points of about 400 F. and endboiling points of about 700 F. In the operation of Diesel engines with such petroleum fuel oils various difficulties arise. Often varnish or gum forms on the piston surfaces, cylinder walls, valves, and atomizing apparatus of Diesel engines operating on such fuel oils, and the piston rings stick. Gum formation on the close fitting pintle valve of the fuel injection equipment results in a rapid drop in power and fluctuating combustion pressure due to inconsistent fuel injection. After several days of operation on ordinary Diesel fuel oils power output and engine efiiciency decrease and there is a noticeable amount -of knocking when the speed of the engine is increased. The engine must frequently beoverhauled, cleaned and adjusted to restore its operating efliciency. Diesel fuel oils used in operating marine Diesel engines often become contaminated with water. As little as 0.1 per cent of water in a Diesel fuel oil can cause corrosion of fuel injectors so serious that the injectors must necessarily be replaced. With certain straight-run light Pennsylvania type fuel oils the wear .on the injectors and plungers is sufficient to render them inaccurate after a few days operation, thereby causing erratic engine performance. In particular, small and medium size Diesel engines which usually operate on rather light fuel oils operate with lessened efficiency because of insufficient lubrication and of corrosion of parts.

terior cylinder surfaces and piston rings appear to be the major causes for the lessened eihciency with which Diesel engines perform when they are operated on ordinary Diesel fuel oils.

It is an object of this invention to manufacture fuel oils for Diesel engines which will improve the power output and performance characteristics of such engines. A further object is to produce Diesel fuel oils which will deposit very little varnish or gum on the engine parts. A still further object is to provide Diesel fuel oils which will not corrode engine parts if said oils become contaminated with water. Another object is to provide Diesel fuel oils which will tend Corrosion, wear and gum formation. on the high pressure injection pumps, in-' 2 to lessen the wear on the engine parts. objects will appear hereinafter.

These objects are accomplished in accordance with the present invention by making improved Diesel fuel oils which contain a small proportion Other of aliphatic amine salts made from a long chain fuel oils.

The aliphatic amine salts used in our improved Diesel fuel oils are made from primary aliphatic amines having at least 10 carbon atoms and the mixture of fatty acids obtained by hydrolyzing sperm oil. The normal straight chain primary aliphatic amines used in preparing the amine salts used in the present'invention preferably contain from 10 to 20 carbon atoms. Usually normal straight chain primary alkyl amines, such as decyl amine, undecyl amine, dodecyl amine, tetradecyl amine, cetyl amine, octadecyl amine and eicosyl amine, are employed, but it isalso permissible to use unsaturated straight chain primary aliphatic amines, such as undecenyl amine, and 9,10-octadecenyl amine (also called oleyl amine). Mixtures of the straight chain primary alkyl amines, such as cocoamine, are often used because of their relative cheapness. Cocoamine is a commercial mixture of higher alkyl amines prepared from coconut oil fatty acids. It contains a major amount of primary dodecyl amine, and typical samples thereof have been found to have average molecular weights ranging from 200 to 210.

The aliphatic amine salts used in our improved Diesel fuel oils are made by reacting approximately equimolecular proportions of amines, such as those mentioned in the-preceding paragraph,

with the mixture of fatty acids obtained by hydrolyzing sperm oil. One of the amine salts by dissolving 10 parts by weight of a mixture of fatty acids and aliphatic alcohols obtained by hydrolyzing sperm oil in 90 parts by weight of a Texas oil having a viscosity of 1200 S. U. V. at 100 F. and then adding from 3 to 5 parts by weight of cocoamine to this solution to neutralize the fatty acids contained therein. A Diesel fuel addition agent prepared in this manner has the following properties:

Gravity, API 21.7 Viscosity, SUV:

100 F 1490 210 F 84.7 Flash, C, 470 Fire, 0C, F 510 P' ur, F +10 From 0.1 per cent to 1 per cent by volume of this Diesel fuel addition agent may be blended with an ordinary Diesel fuel oil in making the improved Diesel fuel oils comprehended by the present invention. Preferably 0.5 per cent by volume of this Diesel fuel addition agent is blended with an ordinary Diesel fuel oil in making the improved Diesel fuel oils of the present invention. The improved Diesel fuel oils of the present invention may contain as little as 0.01 per cent by weight or as much as 0.25 per cent by weight, and preferably contain at least 0.05 per cent by weight of the aliphatic amine derivatives of hydrolyzed sperm oil described above. If desiredwe may dispense entirely with the Texas oil of 1200 SUV at 100 F., and add the aliphatic amine derivatives of hydrolyzed sperm oil directly to the Diesel fuel oil in the desired proportions.

The following table gives the comparative properties of a light Diesel fuel oil and an improved light Diesel fuel oil of the present invention which was made therefrom by blending 0.5 per cent by volume of the Diesel fuel addition agent described in the Preceding paragraph with 99.5 per cent by volume of the light Diesel fuel oil.

With Con- Without eentrate Concentrate Gravity, API 42. 5 42. 6 Viscosity, SUV, 100 F 31 31 Flash, P-M, ASTM D9342, F. 146 146 Pour, F 50 -45 Sulfur, per cent 0. 05 0, 05 Carbon Residue, per cent trace trace Carbon Residue on 10% Bottom, per

cen trace trace Corrosion Test No. l of Patent No. 2,371,853. Distilled water, 36 Ca, 12 days, Steel Strip:

Appearance bright rust Area rusted, per cent...-. m] 100 Neutralization N o nil n11 Acid Heat, ASTM D481-39, F 2 2 Aniline Point, ASTM D01l-44'l, F... 145 145 Diesel Index N 0 61. 7 61. 7 Cetane No. (CFR Ignition Delay The Diesel fuel oils of the present invention such, for example, as that described in the preceding table, display many advantages over ordinary Diesel fuel oils. The close flitting pintle valves in the injection equipment of Diesel engines burning our improved fuel oils do not become covered with gum or corroded, and therefore the combustion pressure and power output remain constant even after more than 1000 hours of operation. This is an important advantage especially in connection with the operation of marine Diesel engines such as those used in power barges. Our new Diesel fuel oils substantially prevent corrosion and wear of the high pressure injection pumps, interior cylinder surfaces and piston rings, and reduce the tendency for piston rings to stick. Our Diesel fuels thus improve markedly the performance of Diesel engines, particularly those of small and medium size that usually operate on rather light fuel oils. The Diesel oils of the present invention decrease the tendency toward ring sticking and varnish formation on cylinder walls, valves and atomizing apparatus, thereby improving engine performance, power output and engine efficiency. The speed of Diesel engines burning our improved fuel oils may be increased with less knocking, and such engines will operate for a longer running time without having to be overhauled. If our Diesel fuel oils become contaminated with a little water, no serious corrosion of the injectors will ensue, since the addition agents added to our fuel oils increase water tolerance. The wear on the plungers and injectors decreases considerably when our fuel oils are employed. Our improved Diesel fuel oils successfully counteract many of the factors that decrease the efliciency of Diesel engines operating on ordinary Diesel fuels.

Resort may be had to such modifications and variations as fall within the spirit of the invention and the scope of the appended claims.

What we claim is: I

1. An improved Diesel fuel oil which consists of Diesel fuel oil and from about 0.01 per cent to about 0.25 per cent by weight of the product obtained by neutralizing the mixture of fatty acids and alcohols contained in hydrolyzed sperm oil with a long chain primary aliphatic amine that has at least 10 carbon atoms.

2. An improved Diesel fuel oil which consists of Diesel fuel oil and about 0.05 per cent by weight of the product obtained by neutralizing the mixture of fatty acids and alcohols contained in hydrolyzed sperm oil with cocoamine.

HERSCHEL G. SMITH. TROY L. CANTRELL. MARK L. HILL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,330,524 Shields Sept. 28, 1943 2,344,016 Anderson Mar. 14, 1944 2,401,993 Wasson June 11, 1946 

